Vat dyestuff and process for making same



Patented Feb. 24, 1925.

- UNITED STATES 1, 9 PATENT OFFICE.

WILHELM MOSER AND HUGO sIEBENBfincER, or BASEL, SWITZERLAND, AssIqNons To THE SOCIETY or CHEMICAL INDUSTRY IN BASLE, or BASEL, SWITZERLAND.-

VAT DYEs'rUFF AND PROCESS FOR MAKING SAME,

No Drawing.

To all whom it may concern:

Be it known, thatwe," VVILHELM Mosnn, citizen of the German Republic, and HUGO SIEBEN I'iRCER, acitizen of the Swiss Republie, bot-h residing at Basel, Switzerland, have invented a new and useful Vat Dyestuff and Process for Makingthe Same, of which the following is a full, clear, and exact specification. I

10 The present inventionrelates to anew Vat dyestuif. The invention" comprisesthe new dyestuff, the process for making the same, as.

welflf as the material. dyed with the new dye- It has-"beenfound'that a new vat dyestuif canbe obtained by treating the 2-aminoanthraquin0ne-3-carboxylic acid .with caustic alkalies, preferably in the presence of an organic fluxi'ng material, for example alcohol,

paraifin, glycerine, aniline, xylidine, and the like, and then subjecting the product of reaction to apurifying rocess. ing process may be e ected in' the follow- 111g manner; 1

and the new dyestuff is most probably to be considered as the 3:3-dicarboxylic acid of the N-dihydro-l 2, l": 2-an thraquinonea zine. I

E trample 1.

10 parts of 2-aminoanthraquinone-3-carboxylic acid are introduced, at 200 to 210 CQ into 30 parts of melted caustic potash. The' mass is then heated for 4 to hour,

while stirring, to- 210 to 230 C. The fusion mass obtained is boiled with water, whereby the dyes'tufl, mixed with other substances, is

precipitated. It is separated by suction and washed. y I V The raw product thus obtained is heated to boiling with dilute nitric acid and kept at the boiling temperature for hour.- The color changes from, blue-black via yellow green to red-brown. The cooled liquid of This purifyapplication filed December 11,-1923. Serial No. 680,034.

. (at) by. treating the raw product with strong sulphuric'acid;

(b) by treating the raw product with oxidizing agents and then with alkalies; (c) by treating the raw product with alkaline reducing agents and separation of the hydro compound. i

, There is thus obtained a new dyestuif which forms a. black-blue powder having a slight copper lustre. It dissolves in concentrated sulphuric acid to an olive solution, in oleum to aye'llow-brown solution, and is pre- -'cipitate'd from these two solutions. by means of water in the form of bright greenish-blue flocks. In nitrobenzene it is but sparingly soluble toa yellow solution. With hydrosulphite it. yields a black-blue vat from which cottonisdyed in clear green-blue tints of quitel preminent. fastness to washing, to

chlorine, light. 45

.The' formationg of the d estufli' most prob ably occurs according to mary equation:

eyfollowing sum- 10 parts of Q-aminoanthraquinone-3-carboxylic acid are introduced, at 900 to 210 G, into 30 parts of melted caustic potash. The mass is then heated for A; to" hour, while stirring, to 210 to 230 C. YThe fusion mass obtained .is boiled with water, whereby the dyestufl, mixed with other substances, is precipitated. It is separated by suction and washed.

from chlorine.

The product thus obtained is made into a paste to which some caustic soda. solution is added. The mass is warmed to about &0" C. and dissolved by adding the necessary quantity of hydrosulphite. The temperature .ismaintained at 40 C. for one hour to 1% hours. From the blue-black vat the hydrocompound-soon separates. The latter is filtered off and free from soluble by-products by washing with alkaline water under addition'of some hydrosulphite. The pure hydrocompound'is then suspended in water, a current of air' blown through, filtered, washed, and dried. 1

c Example 3 80 parts of caustic potash and IOOpa-rts of .alcoholare heated in a vessel provided with a descending cooler, while stirring, until the interior temperature has reached 140 to 145 C. and a homogeneous, clear fusion mass has been. obtained. There are then added 20 parts of Qraminoanthraquinonc-3-carboxylic acid and the stirring continued for one hour at 140 to 150 G.- The fusion mass obtained is boiled with water whereby thedyestuff separates. The mass is then filtered, washed, and dried.

The dried raw dyestufi' is suspended in nitrobenzene, the dyestufi suspension heated to 140 to 145 C. and a moderate current of chlorine gas passedthrough at this tempera-.

ture, whereby transformation into ayellow product occurs. Aftercooling the product is filtered, washed first with nitrobenezene and then with alcohol, and then suspended in water. 'The suspension is mixed, as indicated in Example 1, with caustic soda solu tion or soda, respectively, and boiled, where'- by the blue-black dyestuifis re-formed. By

' filtration and thorough washing the dyestufi' is freed from alkali-soluble by-products and then dried. The

If, in this example, the chlorine is-substituted by the corresponding quantity of antimony pentachloride, the same result is obtained.

Example 4.

20 parts of 2-aminoanthraquinone-id-carboxylic acid are boiled in a reflux apparatus for one hour with 20 parts of caustic potash product obtained is free tration of 90 per cent. The temperature must not be allowed to rise above 90 C. during this operation. After cooling the product is filtered and washed, first with sulphuric acid of 7 0-80. per cent strength, and then with water, and dried.

Example 5. 40 parts of Q-aminoahthraquinone-3-carboxylic acid are introduced, portion by portion, into a fusion mass of 160 parts of caustic potash mixed with 10 parts of aniline, heated to 170 C. The temperature is raised to 180 C. and the mass is stirred during one hour at 180 to 185 C; The fusion is poured into water and the dyestufl' precipitated by boiling. It isthen filtered, washed with water. and dried.-

10 parts of the dyestuff thus obtained are dissolved in 100 parts of monohydrate and slowly'mixed with so much Water that the concentration ofthe sulphuric acid finally reaches 85 per cent whereby care must be taken that'the temperature does not exceed 90 C. The pure dyestufi" separates in form of small, blue needles having a copper lustre. It is isolated as indicated in Example 4:.

Whatwe claim is: v 4 v 1. As a new process the herein described manufacture of a new vat dyestufi, consisting in fusing the 2-aminoanthraquinone-3- .carboxylic acid with caustic alkalies, and then subjecting the product of reaction to a purifying process.

2. As a new process the herein described manufacture of a new 'vat dyestuff, cons-isting in fusing the 2-aminoanthraquinone-3- carboxylic acid with caustic alkalies in the presence of an organic fluxing material, and then subjecting the product of reaction to a purifying process.

3. As a new process the herein described manufactureof a new vat dyestuif, consisting in fusing the 2-aminoanthraquinone-3- carboxylic acid with caustic alkalies in the presence of an aromatic amine, and then subjecting the product of reaction to a purifying process. I

4. 'As a new process the herein described manufacture of a new vat dyestufl, consisting in fusing the 2-aminoanthraquinone-3- carboxylic acid with caustic alkalies in the presence of a primary aromatic amine, and then subjecting the product of reaction to a purifying process.

5. As anew process the herein described manufacture of a new vat dyestuff, consist 'ing in fusing the 2-aminoanthra'quinone-3- carboxylic acid with caustic alkalies in the presence of a primary aromatic amine, and then treating the product of reaction with strong sulphuric acid. I

6. As a new process theherein described manufacture of a new vat dyestufi, consisting in fusing the 2-aminoanthraquinone-3- carboxylic acid with caustic alkalies in the hydrate; and separating the same again by diluting the nonohydrate with water under avoidance of too great a rise of the temperature.,

7. As a new product the herein described new vat dyestufi which most probably is to be considered as the 3:3-diearb0xylic acid of the N-dihydro-l 2, 1 2-anthraquinoneazine, which forms a black-blue powder having a slight copperlustre, dissolving in concentrated sulphuric acid to an olive, and in oleumvto a yellow-brown solution, separating therefrom with water as bright greenish-blue flocks, only sparingly soluble in nitrobenzene to a yellow solution, yielding with hydrosulphite and caustic soda solution a black-blue vat from which cotton is dyed in clear green-blue tints of quite prominent fastness to washing, to chlorine, and to light,

In witness whereof we have hereunto signed our names this 24th day of November, 1923, in the presence of two subscribing witnesses.

- \VILHELM MOSER.

GO sIEBEuBURGER; Witnesses:

AMAND BAUM,

LUCIEN PICARD. 

